Computational and Theoretical Chemistry最新文献

{"title":"Boronate ester-based covalent organic framework as a porous biosensor for anticancer and anti-inflammatory agents: A DFT study on curcumin and crizotinib","authors":"Mubeen Naz ,&nbsp;Muhammad Rafiq ,&nbsp;Muhammad Yar ,&nbsp;Khurshid Ayub ,&nbsp;Sohail Khan ,&nbsp;Jesus Vicente de Julián-Ortiz ,&nbsp;Nadeem S. Sheikh ,&nbsp;Haydar Mohammad-Salim","doi":"10.1016/j.comptc.2025.115394","DOIUrl":"10.1016/j.comptc.2025.115394","url":null,"abstract":"<div><div>This study explores the potential of boronate ester-based COF-1 as a biosensor for anticancer and anti-inflammatory drugs, specifically curcumin and crizotinib, using Density Functional Theory (DFT). Interaction energies, NCI, QTAIM, EDA, and FMO analyses indicate that van der Waals forces mainly govern adsorption. Crizotinib exhibits stronger binding, greater charge transfer, reduced HOMO-LUMO gap, and higher dipole moment, enhancing sensor selectivity and conductivity. Recovery time analysis suggests faster desorption of crizotinib, supporting its suitability for real-time sensing. Overall, COF-1 shows promise as an effective sensor, especially for crizotinib, with applications in drug monitoring and biomedical diagnostics.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115394"},"PeriodicalIF":3.0,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144704578","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comprehensive theoretical analysis of gabapentin antiepileptic adsorption on pristine and Al-doped boron nitride nanotubes surface as a drug delivery vehicle: A DFT study","authors":"Mohammad Rizehbandi ,&nbsp;Farahnaz Davoodi ,&nbsp;Mahdiye Ghasemi ,&nbsp;Shahrzad Javanshir","doi":"10.1016/j.comptc.2025.115381","DOIUrl":"10.1016/j.comptc.2025.115381","url":null,"abstract":"<div><div>In this study, the interaction between the drug gabapentin and boron nitride nanotubes (BNNTs) was investigated, along with the effect of aluminum doping (Al-BNNTs). Using density functional theory (DFT) calculations, key properties such as structural parameters, energy gap, dipole moment, and density of states (DOS) were analyzed for four different configurations of drug adsorption onto the BNNT surface. The results revealed that the angle of molecular approach and the alignment of the drug's dipole moment are significant. From a chemical perspective, the dominant interactions in the pristine BNNT-drug complexes are noncovalent in nature, including van der Waals forces and hydrogen bonding. However, aluminum doping promotes the formation of covalent or semi-covalent bonds, especially between the aluminum atom and functional groups of gabapentin, leading to enhanced structural stability. Additionally, doping was found to reduce the energy gap, introduce mid-gap states near the Fermi level, and improve surface conductivity. We explored optimized geometries, adsorption energies, quantum molecular descriptors, topological parameters, and frontier molecular orbitals of different drug configurations on GBP/BNNTs and GBP/Al-BNNTs at the B3LYP/6–31 + G(d) level of theory in gas phases. To further investigate the nature of these interactions, Reduced Density Gradient (RDG) analysis was used to visualize weak noncovalent forces, and Natural Bond Orbital (NBO) analysis provided insight into charge transfer (CT) and bond hybridization mechanisms. Moreover, doping reduced the energy gap, introduced mid-gap states near the Fermi level, and improved surface conductivity, as confirmed by DOS plots. These findings highlight the potential of Al-doped BNNTs as effective nanocarriers for drug delivery applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115381"},"PeriodicalIF":3.0,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144704495","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First-principles study on the stability of different coordination structures of manganese (II) -pyrimidine complexes","authors":"Haizhen Song,&nbsp;Mengyu Guan,&nbsp;Ranran Bu,&nbsp;Yan Zhang,&nbsp;Yichao Wang,&nbsp;Hongming Yin","doi":"10.1016/j.comptc.2025.115395","DOIUrl":"10.1016/j.comptc.2025.115395","url":null,"abstract":"<div><div>The oriented design of transition metal complexes is a cutting-edge topic in modern coordination chemistry, among which manganese (II) [Mn (II)] pyrimidine complexes have attracted much attention in the development of novel luminescent materials due to their low cost and high luminescence quantum yield. In this study, the unique stability mechanism of the N1 coordination isomer in 2-amino-4-methylpyrimidine-Mn (II) complexes is revealed for the first time by multiscale calculations. Existing Mn (II) - pyrimidine systems mostly focus on the tetrahedral configuration and luminescence properties, whereas systematic quantification of the selectivity of the ligand sites has not been reported. In this study, the stability of three coordination isomers (N1, N2 and N3) of Mn (II) complexes was investigated using first-principles calculations. Geometry optimisation results show that the N1 isomer has the lowest total energy (−837.38 eV) and its planar ligand configuration (dihedral angle 176.177°) effectively maintains the planarity of the π-conjugated system. Hirshfeld surface analysis reveals that the stability of N1 is due to the synergistic effects of strong ionic bonding (Mn - Cl, 4.9 %), oriented π-π stacking (C···C, 4.6 %) and a dense hydrogen bonding network (N - H···N, 10.9 %). It is emphasised that in complex systems the overall structural integrity can easily outweigh the enthalpic contribution of individual stronger coordination bonds. Electronic structure calculations show that the indirect bandgap of N1 is 1.7975 eV (5.8 % deviation from the experimental value), the conduction band/valence band k-space separation is related to the 400 nm Stokes shift phenomenon, the Mn - 3d orbital spin splitting (1.8 eV) dominates the band-side state distribution, and the symmetric hybridisation of the C/N - 2p orbitals promotes the carrier precipitation. These findings establish the design principle of \"ligand symmetry-orbital hybridization\", which provides a new strategy for the development of highly efficient manganese-based phosphorescent materials; the multi-scale framework (structure optimization → surface analysis → electronic calculations) is universal in transition metal complex engineering, which provides a quantitative pathway for the development of manganese-based materials in fields such as bioimaging and optical communications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115395"},"PeriodicalIF":3.0,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144702359","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"On inhibitor reaction pathway with corrosive species and iron surface: Mechanistic and reactive simulation","authors":"Mustafa M. Kadhim ,&nbsp;Anees A. Khadom ,&nbsp;Talib Zeedan Al-Mosawi ,&nbsp;Waleed Khalid Al-Azzawi ,&nbsp;Ahmed A. Al-Amiery","doi":"10.1016/j.comptc.2025.115389","DOIUrl":"10.1016/j.comptc.2025.115389","url":null,"abstract":"<div><div>The performance of Z-3,7-dimethylocta-2,6-dien-1-yl isobutyrate (DDI) as a corrosion inhibitor for steel alloys in the presence of different corrosive species was investigated. Different computational approaches were applied to monitor the electronic and geometric properties and conduct molecular dynamic simulations with Gaussian 16 and Forcite. Several parameters were monitored to optimize the interaction with the substrate, in this case, carbon Steel. The chemical calculations by the DFT methods at the B3LYP/6–311++G (d, p) level proved the presence of distinct electronic properties with the highest occupied molecular orbital (HOMO) of 0.34688 eV. These interactions reflect the formation of stable adsorption layers with varying efficiencies. The highest adsorption heat was observed during the interaction with hydrogen ions, which was followed by the chloride and hydroxide ions with 114.186 kcal/mol. Dynamic simulations utilizing the COMPASSIII force field further confirmed the system goes to a stable state and the inhibitor distribution on the iron surface attains a quasi-homogeneous character, which increases the corrosion mitigation potential. These results are indicative of the effectiveness of DDI as a corrosion inhibitor in different industrial applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115389"},"PeriodicalIF":3.0,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144704496","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First-principles calculations to investigate the oxygen deficiency effect on optoelectronic and mechano-thermoelectric properties of BaTiO3-δ (δ = 0, 0.5, 1)","authors":"I. Ait Elkoua,&nbsp;R. Masrour","doi":"10.1016/j.comptc.2025.115393","DOIUrl":"10.1016/j.comptc.2025.115393","url":null,"abstract":"<div><div>In our study of cubic perovskite materials, we employed the plane wave full-potential linearized augmented plane wave (FP-LAPW) method, grounded in density functional theory (DFT), as implemented in the WIEN2k software package, to determine the crystallographic, electronic, and optical properties of <span><math><msub><mtext>BaTiO</mtext><mrow><mn>3</mn><mo>−</mo><mi>δ</mi></mrow></msub></math></span> (<span><math><mi>δ</mi></math></span> = 0, 0.5, 1) compounds. Various GGA methods treat the potential for exchange and correlation. Barium titanate <span><math><msub><mtext>BaTiO</mtext><mn>3</mn></msub></math></span> is well-known for its interesting electronic properties, particularly its ferroelectric behavior. The oxygen deficiency in this material changes their electronic behavior BaTiO₃, BaTiO_2.5, and BaTiO₂ are promising materials for optical applications in the visible and UV spectra. Furthermore, as oxygen deficiency increases, hole mobility increases as well, enhancing both the optical and electrical conductivities. BaTiO₃ exhibits typical insulating behavior with a well-defined band gap equal to 1.84 eV by GGA method. BaTiO_2.5 shows characteristics of a semiconductor or a narrow-gap insulator equal to 0.37 eV by GGA method, with an increased density of states near the Fermi level, and BaTiO₂ displays metallic behavior. Finally, based on the results obtained using both methods, it can be concluded that the band gap energy is inversely proportional to the oxygen vacancy concentration.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115393"},"PeriodicalIF":3.0,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144704579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The influence of defect for H2O adsorption behavior on tricalcium silicate (001) surface: A DFT study","authors":"Hongping Zhang ,&nbsp;Pengfei Tang ,&nbsp;Kun Yang ,&nbsp;Laibao Liu ,&nbsp;Qingyuan Wang ,&nbsp;Huilong Dong","doi":"10.1016/j.comptc.2025.115391","DOIUrl":"10.1016/j.comptc.2025.115391","url":null,"abstract":"<div><div>Water/tricalcium silicate (C₃S) interaction is critical in the initial stage of C₃S hydration. Adequate research on water-C₃S interaction at the atomistic scale is still lacking. Here, using the density functional theory, we explore the effects of a series of surface defects of C₃S (001) on water adsorption. The surface defects under investigation include Ca or O vacancy, Mn substituted Si, and Mn substituted <em>Ca.</em> It indicates that the interaction between H₂O and C₃S (001) varies with the different interaction mechanisms (adsorption or dissociation adsorption). Electron transfer between H₂O and C₃S (001) surfaces exists no matter whether the water is dissociated or not, and there are more electrons transferred in dissociated systems. The surface-dissociated O and Ca or doped Mn atoms on C₃S (001) have a significant impact on the acceleration of water dissociation. The findings provide a valuable fundamental understanding of the C₃S hydration at the atomistic scale.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115391"},"PeriodicalIF":3.0,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144702357","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigating the influence of vacancy and rhodium doping on nickel-based single-atom catalysts for methane dehydrogenation: A Brønsted–Evans–Polanyi analysis via density functional theory","authors":"Azadeh Jafarizadeh ,&nbsp;MohammadAli Ahmadzadeh ,&nbsp;Masoud Panjepour ,&nbsp;S. Javad Hashemifar","doi":"10.1016/j.comptc.2025.115385","DOIUrl":"10.1016/j.comptc.2025.115385","url":null,"abstract":"<div><div>This study used Density Functional Theory (DFT) to investigate how surface vacancies and Rhodium (Rh) doping affect methane dehydrogenation on Ni(111)-based surfaces. Four surface models were examined: pristine Ni(111), Rh-doped Ni(111), Ni(111) with a vacancy, and Rh-doped Ni(111) with a vacancy. The results revealed that surface vacancies significantly reduce the activation energy for CH decomposition, which promotes carbon accumulation (coke formation) at defect sites. Conversely, Rh doping increases the activation energy for the final CH dissociation step, thereby improving the surface's resistance to amorphous carbon deposition. Notably, combining Rh doping with a vacancy partially mitigates the coke-promoting effect of the defect, although its performance is still not as good as Rh-doped defect-free surfaces. Additionally, a consistent Brønsted–Evans–Polanyi (BEP) relationship was established across all surface models, enabling reliable prediction of activation barriers based on reaction enthalpies. Overall, Rh-doped, defect-free Ni(111) surfaces are identified as the best design for coke-resistant catalysts.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115385"},"PeriodicalIF":3.0,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144696880","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of the C/F/S/O/H ReaxFF force field for the pyrolysis of PFHxS","authors":"Hao-Long Su ,&nbsp;Fang-Chao Hou ,&nbsp;Xiao-Hong Wu ,&nbsp;Ze-Chun Lin ,&nbsp;Zheng Mei ,&nbsp;Chong-Chong She ,&nbsp;Li-Xiao-Song Du ,&nbsp;Jing Sun ,&nbsp;Liang Song","doi":"10.1016/j.comptc.2025.115388","DOIUrl":"10.1016/j.comptc.2025.115388","url":null,"abstract":"<div><div>The pyrolysis mechanism of perfluorohexane sulfonic acid (PFHxS) is crucial for the harmless treatment of PFHxS. Herein, a ReaxFF reactive force field for PFHxS was developed, and ReaxFF molecular dynamics simulations were applied to study the pyrolysis behavior of PFHxS in the temperature range of 1500–3500 K. The homolytic cleavage of C<img>C bonds adjacent to the head group and the breakage of C<img>S bonds are predominant, accounting for 36 % and 27 % of the reactions, respectively. The final products of the pyrolysis of the tail group (-C₆F₁₃) are CF₂ and CF₃. As the temperature rises, the rate of defluorination increases, leading to higher yield of HF and CF₄. Higher temperatures promote the formation of CF₂O and CFO. CF₂ reacts with other intermediates in the free radical pool to form species such as CF₂O and CFO. Initially, HSO₃ and SO₂ are the main carriers of sulfur, and SO₃ contributes less.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115388"},"PeriodicalIF":3.0,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144702358","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Light-induced sensing characteristics of Silicene nanoribbon based device: a first-principles study","authors":"Shazia Showket ,&nbsp;Khurshed A. Shah ,&nbsp;G.N. Dar","doi":"10.1016/j.comptc.2025.115384","DOIUrl":"10.1016/j.comptc.2025.115384","url":null,"abstract":"<div><div>A major drawback of traditional sensors is their sluggish recovery time, which hinders their use in real-time sensing applications. This study introduces a novel optoelectronic approach for benzene (C₆H₆) detection using armchair and zigzag silicene nanoribbons (ASiNR and ZSiNR) under varying photon energies (0–5 eV) to investigate the electronic, charge transport and photo response behavior, via first-principles density functional theory (DFT) and non-equilibrium Green's function (NEGF) formalism. Our findings reveal that the hydrogen-edge passivated ASiNR and ZSiNR exhibit semiconducting and quasi-metallic band structures respectively. Upon benzene adsorption, the electronic and transport properties of silicene nanoribbons undergo significant modulation, resulting in substantial conductivity changes, as confirmed by I-V characteristics and transmission spectra. The strong adsorption energy of benzene (up to −0.93 eV for ASiNR and −0.87 eV for ZSiNR in the dark) ensures stable detection. At the same time, UV irradiation drastically reduces recovery times by up to 99.9 %, enabling rapid sensor regeneration. Furthermore, ZSiNR exhibits superior photocurrent response, making it a highly efficient candidate for optoelectronic VOC sensing. These results establish silicene nanoribbons as promising platforms for next-generation gas sensors, leveraging photon-assisted mechanisms for ultra-sensitive and highly responsive VOC detection at sub-ppb concentrations.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115384"},"PeriodicalIF":3.0,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144696879","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic insights into NiMn bimetallic synergy driving efficient CO₂ to CH4 conversion","authors":"Hedan Yao,&nbsp;YuChen Niu,&nbsp;Hengrui Li,&nbsp;Wenhong Li,&nbsp;Liuyi Pan,&nbsp;Dong Li","doi":"10.1016/j.comptc.2025.115382","DOIUrl":"10.1016/j.comptc.2025.115382","url":null,"abstract":"<div><div>CO₂ methanation represents a critical strategy to address environmental and energy challenges, though its reaction mechanism remains poorly understood. This study establishes a Mn-doped Ni (1 1 1) bimetallic catalytic model and employs density functional theory (DFT) calculations to systematically elucidate the unique mechanism of Ni<img>Mn synergistic effects. At the CO₂ activation stage, Mn doping shortens the metal-O bond length from 2.34 Å to 2.08 Å and alters the active site charge from +0.036 e to −0.147 e, enhancing CO₂ adsorption and dissociation through d-orbital hybridization and charge redistribution. Concurrently, geometric modulation of Ni electronic structures reduces the rate-determining step activation energy to 1.28 eV. Through comparative analysis of three reaction pathways (CO₂^⁎ dissociation followed by CO^⁎ hydrogenation, HCOO^⁎ intermediate reduction, and COOH^⁎ intermediate reduction), the optimal reaction channel has been identified. This work provides theoretical guidance for designing efficient CO₂ conversion catalysts and offers predictive insights for subsequent experimental validation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115382"},"PeriodicalIF":3.0,"publicationDate":"2025-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144702241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}